KR20000034148A - Crosslinking agent for photoresist and photoresist composition using the same - Google Patents

Crosslinking agent for photoresist and photoresist composition using the same Download PDF

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KR20000034148A
KR20000034148A KR1019980051355A KR19980051355A KR20000034148A KR 20000034148 A KR20000034148 A KR 20000034148A KR 1019980051355 A KR1019980051355 A KR 1019980051355A KR 19980051355 A KR19980051355 A KR 19980051355A KR 20000034148 A KR20000034148 A KR 20000034148A
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South Korea
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photoresist
formula
crosslinking agent
poly
triflate
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KR1019980051355A
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Korean (ko)
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KR100400296B1 (en
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정재창
공근규
김명수
김형기
김형수
백기호
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김영환
현대전자산업 주식회사
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Priority to KR10-1998-0051355A priority Critical patent/KR100400296B1/en
Priority to GB9927637A priority patent/GB2344104B/en
Priority to US09/448,916 priority patent/US6368773B1/en
Priority to DE19956531A priority patent/DE19956531A1/en
Priority to FR9914920A priority patent/FR2786491B1/en
Priority to CNB991258568A priority patent/CN1163796C/en
Priority to IT1999TO001042A priority patent/IT1308659B1/en
Priority to NL1013685A priority patent/NL1013685C2/en
Priority to TW088120825A priority patent/TW459010B/en
Priority to JP33865999A priority patent/JP4127941B2/en
Publication of KR20000034148A publication Critical patent/KR20000034148A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking

Abstract

PURPOSE: A crosslinking agent for photoresist is provided which results in remarkable difference of hardening degree of photoresist resin that makes it possible to obtain a photoresist pattern having excellent profile, and in addition it has excellent photosensitivity. Thus, the photoresist using said crosslinking agent is suitable to photolithography using a light source of extremal wavelength region, particularly such as KrF(148 nm), ArF(193 nm), E-beam or EUV light source. CONSTITUTION: The crosslinking monomer for photoresist has the following chemical formula 1, and the polymer thereof have the following chemical formula 2 or 3:(chemical formula 1), (chemical formula 2), (chemical formula 3), wherein R<SB POS="POST">1</SB> and R<SB POS="POST">2</SB> are independently main or branched chain-substituted alkyl having 1 - 10 carbon atoms, and R<SB POS="POST">3</SB> and R<SB POS="POST">4</SB> are independently hydrogen atom or methyl.

Description

신규의 포토레지스트 가교제 및 이를 이용한 포토레지스트 조성물Novel photoresist crosslinking agent and photoresist composition using same

본 발명은 포토레지스트 조성물에 사용되는 가교제 단량체, 그 중합체 및 이를 이용한 포토레지스트 조성물에 관한 것이다. 보다 상세하게는, 고집적 반도체 소자의 미세회로 제작시, KrF(148 nm), ArF (193 nm), E-beam, 이온빔, 혹은 EUV의 광원을 사용한 광리소그래피 공정에 적합한 포토레지스트에 사용되는 가교제 단량체, 그 중합체 및 이를 이용한 포토레지스트 조성물에 관한 것이다.The present invention relates to a crosslinker monomer used in a photoresist composition, a polymer thereof, and a photoresist composition using the same. More specifically, cross-linker monomers used in photoresists suitable for photolithography processes using KrF (148 nm), ArF (193 nm), E-beam, ion beams, or EUV light sources in the manufacture of microcircuits of highly integrated semiconductor devices. The present invention relates to a polymer and a photoresist composition using the same.

반도체 제조의 미세회로 형성 공정에서 고감도를 달성하기 위해, 근래에는 화학증폭성인 DUV(Deep Ultra Violet) 포토레지스트가 각광을 받고 있으며, 그 조성은 광산 발생제(photoacid generator)와 산에 민감하게 반응하는 구조의 매트릭스 고분자를 배합하여 제조한다.In order to achieve high sensitivity in the process of forming microcircuits in semiconductor manufacturing, chemically amplified deep ultra violet (DUV) photoresists have been in the spotlight, and their composition is sensitive to photoacid generators and acids. It is prepared by blending the matrix polymer of the structure.

이러한 포토레지스트의 작용 기전은 광산발생제가 광원으로부터 자외선 빛을 받게 되면 산을 발생시키고, 이렇게 발생된 산에 의해 매트릭스 고분자의 주쇄 또는 측쇄와 가교제 반응하여 가교결합이 생겨서 빛을 받은 부분은 현상액에 녹아 없어지지 않게 된다. 이렇게 하여 마스크의 상을 기판 위에 음화상으로 남길 수 있게 된다. 이와 같은 포토리소그래피 공정에서 해상도는 광원의 파장에 의존하여 광원의 파장이 작아질수록 미세 패턴을 형성시킬 수 있다. 그러나 미세패턴 형성을 위해 노광광원의 파장이 작아 질수록, 즉 193nm 혹은 EUV(extremely UV)사용 할 때는 렌즈가 이 광원에 의해 변형이 일어나게 되고 수명이 짧아지는 단점이 있다.The action mechanism of the photoresist generates acid when the photoacid generator receives ultraviolet light from the light source, and crosslinking occurs by reacting the main chain or side chain of the matrix polymer with the acid generated by the acid, and the lighted part is dissolved in the developer. It won't go away. In this way, the mask image can be left as a negative image on the substrate. In such a photolithography process, the resolution may form a fine pattern as the wavelength of the light source decreases depending on the wavelength of the light source. However, the smaller the wavelength of the exposure light source to form a fine pattern, that is, when the 193nm or EUV (extremely UV) is used, the lens is deformed by this light source has a disadvantage of shortening the life.

통상의 가교제로 사용되고 있는 멜라민(melamine)은 산과 가교가 형성될 수 있는 작용기가 3개로 한정되어 있다. 또한, 가교가 형성될 때 산이 가교 결합에 의해 소비되므로 많은 양의 산을 발생시켜야 하고, 따라서 노광시 많은 양의 에너지가 필요한 단점이 있다.Melamine, which is used as a conventional crosslinking agent, is limited to three functional groups capable of forming crosslinks with acids. In addition, when crosslinking is formed, acid is consumed by crosslinking, so a large amount of acid must be generated, and thus a large amount of energy is required during exposure.

이러한 단점의 극복을 위해서는 보다 강력한 가교제가 필요하고 또한 이 가교제가 화학 증폭형이므로 적은 양의 에너지에도 포토레지스트 수지와 가교가 일어나야 한다. 그러나 이러한 원리의 가교제는 개발되지 않았다.In order to overcome this disadvantage, a stronger crosslinking agent is required, and since the crosslinking agent is a chemically amplified type, crosslinking with the photoresist resin should occur even at a small amount of energy. However, crosslinkers of this principle have not been developed.

한편, 고밀도 패턴에서는 현상액이 가교결합부위에 스며들어, 가교결합부위가 부풀어 오르는 팽윤 현상(swelling)이 나타나므로, 보다 고밀도의 패턴을 형성하기 위해서는 가교결합이 보다 치밀하게 일어나는 새로운 가교제의 도입이 요구된다.On the other hand, in the high-density pattern, the developing solution penetrates the crosslinking site and swelling of the crosslinking site appears. Therefore, in order to form a higher-density pattern, the introduction of a new crosslinking agent with more dense crosslinking is required. do.

도 1은 종래의 가교제를 이용한 포토레지스트 조성물로 패터닝된 포토레지스트 패턴을 보여준다.(J. Photopolymer Science and Technology. Vol.11, No3, 1998, 507 ~ 512). 상기 패턴은 ArF광원을 채용하는 포토리소그래피 공정에 의해 얻어진 0.225㎛ L/S 패턴으로서, 모노머릭 가교제(monomeric crosslinker)를 사용하여 얻어진 것이다.1 shows a photoresist pattern patterned with a photoresist composition using a conventional crosslinking agent. (J. Photopolymer Science and Technology. Vol. 11, No3, 1998, 507-512). The said pattern is a 0.225 micrometer L / S pattern obtained by the photolithography process which employs an ArF light source, and is obtained using a monomeric crosslinker.

도 1에 도시된 바와 같이, 이러한 종래의 포토레지스트 패턴에서는 팽윤 현상(swelling)이 유발되므로, 종래의 포토레지스트 가교제 및 이를 이용한 조성물로는 0.225㎛ L/S 이하의 패턴 형성이 어렵다.As shown in FIG. 1, since swelling is caused in the conventional photoresist pattern, it is difficult to form a pattern of 0.225 μm L / S or less with a conventional photoresist crosslinking agent and a composition using the same.

본 발명은 신규의 포토레지스트용 가교제 단량체 및 그 제조방법을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a novel crosslinking monomer for a photoresist and a method for producing the same.

또, 본 발명은 상기 가교제 단량체를 이용한 신규의 가교제 및 그 제조방법을 제공한다.Moreover, this invention provides the novel crosslinking agent using the said crosslinking agent monomer, and its manufacturing method.

또한, 극단파장 광원을 채용하는 포토레지스트 공정에 적합한 포토레지스트 조성물 및 그 제조방법을 제공하는 것을 목적으로 한다.Moreover, it aims at providing the photoresist composition suitable for the photoresist process employing an extreme wavelength light source, and its manufacturing method.

또한, 상기 포토레지스트 조성물을 이용하여 제조된 반도체 소자를 제공하는 것을 또 다른 목적으로 한다.In addition, another object of the present invention is to provide a semiconductor device manufactured using the photoresist composition.

도 1은 종래의 가교제를 이용하여 제조된 포토레지스트 패턴을 도시한다.Figure 1 shows a photoresist pattern prepared using a conventional crosslinking agent.

도 2는 본 발명에 따른 가교제를 이용하여 제조된 포토레지스트 패턴을 도시한다.Figure 2 shows a photoresist pattern prepared using a crosslinking agent according to the present invention.

상기한 목적을 달성하기 위해, 본 발명은 하기 화학식 1로 표시되는 가교 단량체를 제공한다.In order to achieve the above object, the present invention provides a crosslinking monomer represented by the following formula (1).

＜화학식 1＞<Formula 1>

여기서, R1 및 R2는 각각 탄소수 1 내지 10의 주쇄 혹은 측쇄 치환된 알킬이며, R3는 수소 혹은 메틸이다.Here, R1 and R2 are each C1-C10 main chain or branched-substituted alkyl, and R3 is hydrogen or methyl.

본 발명의 다른 목적을 달성하기 위해, 하기 화학식 2 및 화학식 3으로 표시되는 가교제가 제공된다.In order to achieve another object of the present invention, a crosslinking agent represented by the following formula (2) and (3) is provided.

＜화학식 2＞<Formula 2>

＜화학식 3＞<Formula 3>

또, 본 발명의 또 다른 목적을 달성하기 위해, (i)포토레지스트 수지와, (ii)하기 화학식 1로 표시되는 화합물의 호모중합체 또는 공중합체와, (iii)광산발생제와, (iv)유기용매를 포함하는 포토레지스트 조성물이 제공된다.In order to achieve another object of the present invention, a homopolymer or copolymer of (i) a photoresist resin, (ii) a compound represented by the following formula (1), (iii) a photoacid generator, and (iv) There is provided a photoresist composition comprising an organic solvent.

이하, 구체적인 실시예를 들어, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to specific examples.

본 발명자들은 수많은 실험을 거쳐 하기 화학식 1의 화합물이 네가티브 포토레지스트의 가교 단량체로서 적합한 특성을 갖는 것을 발견하였다.The inventors have conducted a number of experiments to find that the compound of formula 1 has suitable properties as a crosslinking monomer of negative photoresist.

＜화학식 1＞<Formula 1>

여기서, R1 및 R2 는 각각 탄소수 1 내지 10의 주쇄 혹은 측쇄 치환된 알킬이며,Wherein R 1 and R 2 are each C 1-10 C- or C-substituted alkyl,

R3은 각각 수소 혹은 메틸이다.R 3 is hydrogen or methyl, respectively.

상기 화학식 1의 화합물은 산의 존재하에서 수산기(-0H)를 갖는 포토레지스트 수지와 반응하여 상기 포토레지스트 수지간 가교 결합을 유도한다. 또한, 포토레지스트 수지와 결합되면서 다시 산(H+)을 발생시켜 연쇄적인 가교반응을 유도할 수 있는 화학증폭형 가교제이다. 따라서, 포스트 베이크 과정에서 노광부의 포토레지스트 수지가 고밀도로 경화될 수 있으므로 우수한 패턴을 얻을 수 있다.The compound of Formula 1 reacts with a photoresist resin having a hydroxyl group (-0H) in the presence of an acid to induce crosslinking between the photoresist resins. In addition, it is a chemically amplified crosslinking agent capable of inducing acid (H +) while being combined with the photoresist resin to induce a chain crosslinking reaction. Therefore, since the photoresist resin of the exposed portion can be hardened at a high density in the post-baking process, an excellent pattern can be obtained.

따라서, 상기 화학식 1의 가교 단량체를 이용하여 포토레지스트용 가교제로 사용할 경우, 우수한 특성을 갖는 포토레지스트 조성물을 제조할 수 있다. 이러한 가교제는 하기 화학식 2 또는 하기 화학식 3 의 형태를 갖는 것이 보다 바람직한다.Therefore, when used as a crosslinking agent for a photoresist using the crosslinking monomer of Formula 1, it can be prepared a photoresist composition having excellent properties. It is more preferable that such a crosslinking agent has the form of following General formula (2) or following General formula (3).

＜화학식 2＞<Formula 2>

여기서, R1 및 R2 는 각각 탄소수 1 내지 10의 주쇄 혹은 측쇄 치환된 알킬이며,Wherein R 1 and R 2 are each C 1-10 C- or C-substituted alkyl,

R3 및 R4는 각각 수소 혹은 메틸이다. 또, a는 10 내지 100 이고 b는 0 내지 30의 몰 퍼센트 비율로 되는 것이 바람직하다.R3 and R4 are each hydrogen or methyl. Moreover, it is preferable that a is 10-100 and b is 0-30 molar percentage ratio.

＜화학식 3＞<Formula 3>

여기서, R1 및 R2는 각각 탄소수 1 내지 10의 주쇄 혹은 측쇄 치환된 알킬이며, R3는 수소 혹은 메틸이다. 또, a는 10 내지 100 이고, b는 10 내지 100의 몰 퍼센트 비율로 구성되는 것이 보다 바람직하다.Here, R1 and R2 are each C1-C10 main chain or branched-substituted alkyl, and R3 is hydrogen or methyl. In addition, a is 10 to 100, and b is more preferably composed of a mole percent ratio of 10 to 100.

본 발명에 따른 가교제의 반응메카니즘을 하기 반응식 1을 참고하여 설명한다. 하기 반응식 1은 상기 화학식 2의 가교제를 예로 든 것이나, 화학식 3의 경우에도 반응메카니즘은 이와 동일하다.The reaction mechanism of the crosslinking agent according to the present invention will be described with reference to Scheme 1 below. Scheme 1 below is a cross-linking agent of the formula (2) as an example, even in the case of formula (3) the reaction mechanism is the same.

먼저, 본 발명에 따른 가교제와 포토레지스트 수지를 혼합한 후, 소정의 기판상에 도포한다(제1 단계). 이어서, 상기 기판의 소정 영역을 노광하면, 노광부위에서는 산이 발생된다(제2 단계). 노광부위에서 발생된 산으로 인해, 본 발명에 따른 가교제와 포토레지스트 수지는 결합하게 되고, 이러한 가교 결합의 결과, 다시 산이 발생되므로, 연쇄적인 가교 작용이 수행된다(제3 단계).First, the crosslinking agent according to the present invention and the photoresist resin are mixed and then applied onto a predetermined substrate (first step). Subsequently, when a predetermined region of the substrate is exposed, acid is generated at the exposed portion (second step). Due to the acid generated at the exposure site, the crosslinking agent and the photoresist resin according to the present invention are bonded to each other, and as a result of the crosslinking, acid is generated again, so that a chain crosslinking action is performed (step 3).

＜반응식 1＞<Scheme 1>

가교제의 제조Preparation of Crosslinking Agent

이하에서는, 본 발명에 따른 가교제의 제조방법을 구체적인 예로 들어 설명한다.Hereinafter, the manufacturing method of the crosslinking agent which concerns on this invention is demonstrated to a specific example.

실시예 1Example 1

폴리(3, 3 -디메톡시프로펜)의 합성Synthesis of Poly (3,3-dimethoxypropene)

아크로레인(acrolein) 30g, AIBN 0.6g 및 테트라하이드로퓨란 75g을 200 ml 플라스크에 넣은 후 질소 혹은 아르곤 상태에서 65 ℃의 온도로 8시간 반응시킨다. 고분자 반응 완료 후 에틸 에테르 용매에서 고분자 침전을 잡아 폴리아크로레인을 얻었다(수율 60%).30 g of acrolein, 0.6 g of AIBN, and 75 g of tetrahydrofuran were added to a 200 ml flask, and then reacted at a temperature of 65 ° C. under nitrogen or argon for 8 hours. After completion of the polymer reaction, the polymer was precipitated in an ethyl ether solvent to obtain polyacrolein (yield 60%).

얻어진 폴리아크로레인 20g과 메탄올 200g을 500ml 둥근 플라스크에 넣은 후 잘 섞어준다. 여기에 트리프루오르메탄 설폰산 0.5g을 넣고 80 ℃ 에서 24 시간 환류시킨다. 환류 후, 로타리 증류기로 농축시킨 후 증류수에서 침전을 잡아 진공건조하여 하기 화학식4 의 폴리(3, 3-디메톡시프로펜) 수지를 얻었다(수율 60%). 하기 화학식 4의 화합물은 NMR 스펙트럼 관찰 결과, 8 내지 9 ppm 사이에서 나타나는 알데히드 피크(peak)가 사라지는 것으로부터 확인할 수 있다. 또한 하기 화학식 4의 분자량은 4,000 내지 6,000 의 범위에 있는 것이 바람직하다.(GPC로 확인)20 g of the polyacrolein obtained and 200 g of methanol are added to a 500 ml round flask, followed by mixing well. 0.5 g of trifluoromethane sulfonic acid was added thereto, and the mixture was refluxed at 80 ° C for 24 hours. After refluxing, the mixture was concentrated in a rotary distillation, precipitated in distilled water, and dried in vacuo to obtain a poly (3,3-dimethoxypropene) resin of formula 4 (yield 60%). The compound of Formula 4 may be confirmed from disappearance of an aldehyde peak appearing between 8 and 9 ppm as a result of NMR spectrum observation. In addition, the molecular weight of the following general formula (4) is preferably in the range of 4,000 to 6,000 (confirmed by GPC).

＜화학식 4＞<Formula 4>

실시예2Example 2

폴리(3, 3 -디메톡시프로펜/아크릴산)의 합성Synthesis of Poly (3,3-dimethoxypropene / acrylic acid)

하기 화학식 5의 3,3-디메톡시프로펜 30g과, 아크릴 산 3g과, AIBN 0.66g 및 테트라하이드로 퓨란 80g을 200ml 플라스크에 넣은 후, 질소 혹은 아르곤 상태에서 60 ℃의 온도로 8시간 반응 시킨다. 고분자 반응 완료 후 물에서 고분자 침전을 잡아 하기 화학식 6의 폴리(3, 3 -디메톡시프로펜/아크릴산)을 얻었다.(수율 70%, 분자량은 4,000 내지 7,000)30 g of 3,3-dimethoxypropene of Formula 5, 3 g of acrylic acid, 0.66 g of AIBN, and 80 g of tetrahydrofuran were put into a 200 ml flask, and then reacted at a temperature of 60 ° C. under nitrogen or argon for 8 hours. After the polymer reaction was completed, the polymer was precipitated in water to obtain poly (3,3-dimethoxypropene / acrylic acid) of Chemical Formula 6 (yield 70%, molecular weight: 4,000 to 7,000).

＜화학식 5＞<Formula 5>

＜화학식 6＞<Formula 6>

실시예 3Example 3

폴리(3, 3 -디에톡시프로펜)의 합성Synthesis of Poly (3,3-diethoxypropene)

메탄올 대신에 에탄올을 사용하는 것을 제외하고 실시예 1과 동일한 방법으로 하기 화학식 7의 화합물 즉, 폴리(3, 3 -디에톡시프로펜)을 얻었다.(수율67%)Except for using ethanol instead of methanol to obtain a compound of the formula (7), that is, poly (3,3-diethoxypropene) in the same manner as in Example 1. (Yield 67%)

＜화학식 7＞<Formula 7>

실시예 4Example 4

폴리(3, 3 -디에톡시프로펜/아크릴산)의 합성Synthesis of Poly (3,3-diethoxypropene / acrylic acid)

3, 3 -디메톡시프로펜 대신에 3, 3 -디에톡시프로펜 에탄올을 사용하는 것을 제외하고는 실시예 2와 동일한 방법으로 하기 화학식 8의 화합물, 폴리(3, 3 -디에톡시프로펜/아크릴산)을 얻었다.(수율 67%)The compound of formula 8, poly (3,3-diethoxypropene / Acrylic acid) was obtained. (Yield 67%)

＜화학식 8＞<Formula 8>

실시예 5Example 5

폴리(3,3-디메톡시프로펜/말레익안하이드라이드)의 합성Synthesis of Poly (3,3-dimethoxypropene / maleic anhydride)

상기 화학식 5의 3, 3 -디메톡시프로펜 0.3몰과, 말레익 안하이드라이드 0.1몰과, AIBN 0.8g 및 42g의 테트라하이드로퓨란를 100ml 플라스크에 넣은 후 질소 혹은 아르곤 상태에서 65 ℃의 온도에서 8시간 반응시킨다. 고분자 반응 완료 후 에틸 에테르 용매에서 고분자 침전을 잡아 진공건조 하여 순수한 상태로 하기 화학식 9의 수지를 얻었다(수율 50%).0.3 mol of 3,3-dimethoxypropene of Formula 5, 0.1 mol of maleic anhydride, and 0.8 g and 42 g of tetrahydrofuran were added to a 100 ml flask, followed by 8 at a temperature of 65 ° C. under nitrogen or argon. React time. After completion of the polymer reaction, the polymer was precipitated in an ethyl ether solvent, and dried in vacuo to obtain a resin of formula 9 in a pure state (yield 50%).

＜화학식 9＞<Formula 9>

실시예 6Example 6

폴리(3,3-디에톡시프로펜/말레익안하이드라이드)의 합성Synthesis of Poly (3,3-diethoxypropene / maleic anhydride)

상기 화학식 5의 3,3-디메톡시프로펜 0.3 몰 대신에 하기 화학식 10의 3,3-디에톡시프로펜 0.3 몰을 사용하는 것을 제외하고는 실시예 5와 동일한 방법으로 하기 화학식 11의 화합물을 얻었다.(수율 51%)A compound of Chemical Formula 11 was prepared in the same manner as in Example 5 except that 0.3 mol of 3,3-diethoxypropene of Formula 10 was used instead of 0.3 mol of 3,3-dimethoxypropene of Formula 5 (Yield 51%)

＜화학식 10＞<Formula 10>

＜화학식 11＞<Formula 11>

상기 실시예 1 내지 4에서 중합개시제로 AIBN을 사용하고 있으나, 이외에도 라우릴 펄옥시드 등의 기타 통상적인 라디칼 중합 개시제를 사용할 수도 있다.Although AIBN is used as the polymerization initiator in Examples 1 to 4, other conventional radical polymerization initiators such as lauryl peroxide may be used.

또, 중합용매로 테트라하이드록 퓨란을 사용하였으나, 이외에도 프로필렌글리콜, 톨루엔, 메틸에테르 또는 아세테이트 등의 용매를 사용할 수도 있다.In addition, tetrahydroxyfuran was used as the polymerization solvent, but other solvents such as propylene glycol, toluene, methyl ether or acetate can also be used.

포토레지스트 조성물의 제조Preparation of Photoresist Composition

이하에서는, 본 발명에 따른 가교제를 이용한 네가티브 포토레지스트 조성물의 제조방법을 설명한다.Hereinafter, the manufacturing method of the negative photoresist composition using the crosslinking agent which concerns on this invention is demonstrated.

본 발명에 따른 가교제는 화학증폭형 가교제이므로, 본 발명에 따른 포토레지스트 조성물은 (i) 네가티브형 포토레지스트 수지와, (ii) 본 발명에 따른 가교제 외에도, (iii) 광산발생제(acid generator)를 포함하며, 이들 물질들을 혼합시키기 위해 (iv) 유기용매를 사용한다.Since the crosslinking agent according to the present invention is a chemically amplified crosslinking agent, the photoresist composition according to the present invention is in addition to (i) a negative photoresist resin and (ii) a crosslinking agent according to the present invention, and (iii) an acid generator. And, (iv) using an organic solvent to mix these materials.

상기 광산발생제는 황화염계 또는 오니움염계로서, 디페닐요도염 헥사플루오르포스페이트, 디페닐요도염 헥사플루오르 아르세네이트, 디페닐요도염 헥사플루오르 안티모네이트, 디페닐파라메톡시페닐 트리플레이트, 디페닐파라톨루에닐 트리플레이트, 디페닐파라이소부틸페닐 트리플레이트, 디페닐파라-t-부틸페닐 트리플레이트, 트리페닐설포늄 헥사플루오르 포스페이트, 트리페닐설포늄 헥사플루오르 아르세네이트, 트리페닐설포늄 헥사플루오르 안티모네이트, 트리페닐설포늄 트리플레이트, 디부틸나프틸설포늄 트리플레이트 중 1 또는 2 이상을 사용할 수 있다.The photoacid generator is a sulfur salt-based or onium salt-based diphenyl iodo hexafluorophosphate, diphenyl iodo hexafluoro arsenate, diphenyl iodo hexafluoro antimonate, diphenyl paramethoxyphenyl triflate, diphenyl Paratoluenyl triflate, diphenylparaisobutylphenyl triflate, diphenylpara-t-butylphenyl triflate, triphenylsulfonium hexafluoro phosphate, triphenylsulfonium hexafluor arsenate, triphenylsulfonium hexa One or two or more of fluorine antimonate, triphenylsulfonium triflate and dibutylnaphthylsulfonium triflate may be used.

또, 유기용매로는 시클로헥사논, 메틸 3-메톡시프로피오네이트, 에틸 3-에톡시프로피오네이트, 프로필렌글리콜 메틸에테르 아세테이트 또는 기타 통상의 유기용매를 사용할 수 있다.As the organic solvent, cyclohexanone, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether acetate or other conventional organic solvents can be used.

포토레지스트 패턴의 형성Formation of Photoresist Pattern

본 발명에 따라 제조된 포토레지스트 조성물을 실리콘 웨이퍼에 스핀 도포하여 박막을 형성한 다음, 70 내지 200℃ 보다 바람직하게는 80 내지 150℃의 오븐 또는 열판에서 1 내지 5분간 소프트 베이크를 하고, 원자외선 노광장치 또는 엑시머 레이져 노광장치를 이용하여 노광한 후, 10 내지 200℃ 보다 바람직하게는 100 내지 200℃에서 포스트 베이크를 수행한다. 이때, 노광원으로는 ArF광, KrF광, E-빔, X-레이, EUV(extremely ultra violet), DUV(deep ultra violet) 등을 사용할 수도 있으며, 노광에너지는 0.1 내지 100mJ/㎠이 바람직하다.After spin-coating a photoresist composition prepared according to the present invention on a silicon wafer to form a thin film, soft bake for 1 to 5 minutes in an oven or hot plate at 70 to 200 ° C., more preferably 80 to 150 ° C., and After exposing using an exposure apparatus or an excimer laser exposure apparatus, post-baking is performed at 10-200 degreeC more preferably at 100-200 degreeC. In this case, ArF light, KrF light, E-beam, X-ray, extremely ultra violet (EUV), deep ultra violet (DUV) and the like may be used as the exposure source, and the exposure energy is preferably 0.1 to 100 mJ / cm 2. .

이렇게 노광한 웨이퍼를 알카리 현상액 예를 들어, 2.38% 또는 2.5% TMAH수용액에 일정 시간동안 바람직하게는 1분30초간 침지하여 현상함으로써 초미세 패턴을 얻을 수 있다.The wafer thus exposed is immersed in an alkali developer, for example, a 2.38% or 2.5% TMAH aqueous solution for a predetermined time, preferably for 1 minute and 30 seconds, and developed to obtain an ultrafine pattern.

실시예 7Example 7

(i)하기 화학식 12의 포토레지스트 수지 즉, 폴리(바이싸이크로[2.2.1]헵트-5-엔 / 2-하이드록시에틸바이싸이크로[2.2.1]헵트-5-엔 2-카르복실레이트 / 말레익 안하이드라이드) 20g과, (ii)본 발명의 실시예 1에서 얻어진 상기 화학식 5의 폴리(3, 3 -디메톡시프로펜) 가교제 5g과, (iii) 광산발생제로 트리페닐 설포늄 트리플레이트 0.6g을 (iv) 유기용매인 프로필렌 글리콜 메틸 에테르 아세테이트(propylene glycol methyl ether acetate) 200g에 녹여 포토레지스트 조성물을 제조하였다.(i) a photoresist resin of formula 12, ie poly (bicyclo [2.2.1] hept-5-ene / 2-hydroxyethylbicyclo [2.2.1] hept-5-ene 2-carboxyl 20 g of acrylate / maleic anhydride), (ii) 5 g of a poly (3,3-dimethoxypropene) crosslinking agent of formula 5 obtained in Example 1 of the present invention, and (iii) triphenyl sulfide as a photoacid generator. The photoresist composition was prepared by dissolving 0.6 g of phosphon triflate in (iv) 200 g of propylene glycol methyl ether acetate as an organic solvent.

＜화학식 12＞<Formula 12>

제조된 포토레지스트 조성물을 실리콘 웨이퍼위에 도포하여 110℃에서 90초 동안 소프트 베이크 한 후, ArF 노광 장비로 노광하고, 이어서 110℃에서 90초 동안 다시 포스트 베이크 한 후 2.38wt% TMAH 현상액으로 현상하였다. 그 결과, 도 2 에 도시된 바와 같은 0.13㎛ L/S의 초미세 네가티브 패턴이 얻어졌다.The photoresist composition thus prepared was applied on a silicon wafer, soft baked at 110 ° C. for 90 seconds, exposed with an ArF exposure apparatus, and then post-baked at 110 ° C. for 90 seconds, and then developed with a 2.38 wt% TMAH developer. As a result, an ultrafine negative pattern of 0.13 mu m L / S as shown in Fig. 2 was obtained.

이때, 조사된 노광 에너지는 18mJ/cm2으로서, 이와 같은 미세한 강도의 노광에너지에서도 포토레지스트 조성물의 경화 감도가 매우 우수함을 알 수 있었다. 또, 도 1에 보여지는 바와 같은 팽윤(swelling) 현상도 관찰되지 않았다. 이는 본 발명에 따른 가교제인 폴리(3, 3 -디메톡시프로펜) 수지의 경화능력이 매우 우수하며, 따라서, 가교결합이 치밀하게 이루어진 것에 기인한다. 따라서, 초미세 패턴에 있어서도 우수한 패턴 프로파일을 나타내고 있다.At this time, the irradiated exposure energy was 18 mJ / cm 2, and it was found that the curing sensitivity of the photoresist composition was very excellent even at the exposure energy of such a small intensity. Moreover, the swelling phenomenon as shown in FIG. 1 was not observed, either. This is attributable to the excellent curing ability of the poly (3,3-dimethoxypropene) resin, which is a crosslinking agent according to the present invention, and thus to a high degree of crosslinking. Therefore, the pattern profile which was excellent also in the ultra-fine pattern is shown.

실시예 8Example 8

(i)상기 화학식 13의 포토레지스트 수지 즉, 폴리(바이싸이크로[2.2.1]헵트-5-엔 / 2-하이드록시에틸바이싸이크로[2.2.1]헵트-5-엔 2-카르복실레이트 /말레익 안하이드라이드) 20g과 , (ii) 상기 실시예 2에서 얻은 폴리(3, 3 디메톡시프로펜/아크릴산) 가교제 20g과, (iii) 광산발생제인 트리페닐 설포늄 트리플레이트 0.7g을 (iv) 유기용매인 프로필렌 글리콜 메틸 에테르 아세테이트(propylene glycol methyl ether acetate) 200g에 녹여 포토레지스트 조성물을 제조하였다.(i) the photoresist resin of Chemical Formula 13, ie, poly (bicyclo [2.2.1] hept-5-ene / 2-hydroxyethylbicyclo [2.2.1] hept-5-ene 2-carboxyl 20 g of acrylate / maleic anhydride, (ii) 20 g of a poly (3,3 dimethoxypropene / acrylic acid) crosslinking agent obtained in Example 2, and (iii) 0.7 g of triphenyl sulfonium triflate as a photoacid generator. (Iv) was dissolved in 200 g of propylene glycol methyl ether acetate as an organic solvent to prepare a photoresist composition.

이렇게 제조된 포토레지스트 조성물을 실리콘 웨이퍼위에 도포하여 110℃에서 90초 동안 소프트 베이크 한 후 ArF 노광 장비로 노광하고 이어서 110℃에서 90초 동안 다시 포스트 베이크 한 후, 2.38wt% TMAH 현상액에서 현상하여 0.13㎛ L/S의 초미세 네가티브 패턴을 얻었다. 이때, 노광 에너지는 상기 실시예 1과 동일하게 15mJ/cm2으로 매우 약했음에도 불구하고 우수한 패턴 프로파일을 갖는 초미세 패턴을 얻을 수 있었다.The photoresist composition thus prepared was applied onto a silicon wafer, soft baked at 110 ° C. for 90 seconds, exposed with an ArF exposure apparatus, and then post-baked at 110 ° C. for 90 seconds, and then developed in a 2.38 wt% TMAH developer to develop 0.13. An ultrafine negative pattern of 탆 L / S was obtained. At this time, although the exposure energy was very weak at 15 mJ / cm 2 as in Example 1, an ultrafine pattern having an excellent pattern profile was obtained.

상기 실시예 3 내지 6에서 얻어진 가교제에 대해서도 동일한 실험을 반복하였으며, 그 결과 실시예 7 또는 8에서 얻어진 바와 같은 우수한 미세패턴이 얻어졌다.The same experiment was repeated for the crosslinking agents obtained in Examples 3 to 6, and as a result, excellent fine patterns as obtained in Example 7 or 8 were obtained.

본 발명에 따른 신규의 가교제를 이용하여 포토레지스트 조성물을 제조하는 경우에, 노광부와 비노광부에서 포토레지스트 수지의 경화정도의 차가 현저해지고, 따라서, 보다 우수한 프로파일을 갖는 포토레지스트 패턴을 얻을 수 있다. 또, 본 발명에 따른 가교제는 화학증폭형이므로, 소량의 광산발생제만을 사용함으로써 충분한 효과를 달성할 수 있어, 광산발생제가 다량 포함됨으로써 유발되는 문제점을 해결하고 있으며, 광 민감성이 뛰어나므로 낮은 노광에너지를 조사함으로써 충분한 노광효과를 달성할 수 있다. 따라서, 초미세패턴, 특히 ArF(193nm)광원과 같은 극단파장 영역의 광원을 채용하는 포토리소그래피에 적합하다.When manufacturing a photoresist composition using the novel crosslinking agent according to the present invention, the difference in the degree of curing of the photoresist resin in the exposed portion and the non-exposed portion becomes remarkable, and thus a photoresist pattern having a better profile can be obtained. . In addition, since the crosslinking agent according to the present invention is a chemically amplified type, it is possible to achieve a sufficient effect by using only a small amount of photoacid generator, thereby solving the problem caused by the inclusion of a large amount of photoacid generator, and excellent light sensitivity, so low exposure Sufficient exposure effect can be achieved by irradiating an energy. Therefore, it is suitable for photolithography employing ultra fine patterns, especially light sources in extreme wavelength regions such as ArF (193 nm) light sources.

Claims (19)

포토레지스트용 가교 단량체로서 사용되는 하기 화학식 1의 화합물.Compound of formula 1 used as a crosslinking monomer for photoresist. ＜화학식 1＞<Formula 1> 여기서, R1 및 R2는 각각 탄소수 1 내지 10의 주쇄 혹은 측쇄 치환된 알킬이며, R3는 수소 혹은 메틸이다.Here, R1 and R2 are each C1-C10 main chain or branched-substituted alkyl, and R3 is hydrogen or methyl. 제1항 기재의 화합물을 포함하는 것을 특징으로 하는 포토레지스트 가교제.A photoresist crosslinking agent comprising the compound of claim 1. 제 2 항에 있어서,The method of claim 2, 상기 가교제는 제1항 기재에 기재된 화학식 1의 화합물의 호모중합체 또는 공중합체인 것을 특징으로 하는 가교제.The crosslinking agent is a homopolymer or copolymer of the compound of formula (1) according to claim 1, characterized in that the crosslinking agent. 제 3 항에 있어서,The method of claim 3, wherein 상기 가교제는 하기 화학식 2 또는 화학식 3의 화합물인 것을 특징으로 하는 가교제.The crosslinking agent is a crosslinking agent, characterized in that the compound of formula (2) or formula (3). ＜화학식 2＞<Formula 2> 여기서, R1 및 R2 는 각각 탄소수 1 내지 10의 주쇄 혹은 측쇄 치환된 알킬이며,Wherein R 1 and R 2 are each C 1-10 C- or C-substituted alkyl, R3 및 R4는 각각 수소 혹은 메틸이다.R3 and R4 are each hydrogen or methyl. ＜화학식 3＞<Formula 3> 여기서, R1 및 R2는 각각 탄소수 1 내지 10의 주쇄 혹은 측쇄 치환된 알킬이며, R3는 수소 혹은 메틸이다.Here, R1 and R2 are each C1-C10 main chain or branched-substituted alkyl, and R3 is hydrogen or methyl. 제 4 항에 있어서,The method of claim 4, wherein 상기 화학식 2의 a는 10 내지 100몰% 이고, b는 0 내지 30몰%이며, 화학식 3의 a 및 b는 각각 10 내지 100몰%인 것을 특징으로 하는 가교제.A in Formula 2 is 10 to 100 mol%, b is 0 to 30 mol%, and a and b in Formula 3 are each 10 to 100 mol% crosslinking agent. 제 3 항에 있어서,The method of claim 3, wherein 상기 가교제는The crosslinking agent 폴리(3, 3 -디메톡시프로펜);Poly (3, 3-dimethoxypropene); 폴리(3, 3 -디에톡시프로펜);Poly (3, 3-diethoxypropene); 폴리(3, 3 -디메톡시프로펜/아크릴산);Poly (3, 3-dimethoxypropene / acrylic acid); 폴리(3, 3 -디에톡시프로펜/아크릴산);Poly (3,3-diethoxypropene / acrylic acid); 폴리(3,3-디메톡시프로펜/말레익안하이드라이드); 및Poly (3,3-dimethoxypropene / maleic anhydride); And 폴리(3,3-디에톡시프로펜/말레익안하이드라이드)로 이루어진 군으로부터 선택된 것을 특징으로 하는 가교제.A crosslinking agent selected from the group consisting of poly (3,3-diethoxypropene / maleic anhydride). (i) 포토레지스트 공중합체와,(i) a photoresist copolymer, (ii) 제1항 기재의 가교 단량체를 이용하여 제조된 가교제와,(ii) a crosslinking agent produced using the crosslinking monomer according to claim 1, (iii) 광산발생제와,(iii) a photoacid generator, (iv) 유기용매를 포함하는 것을 특징으로 하는 포토레지스트 조성물.(iv) A photoresist composition comprising an organic solvent. 제 7 항에 있어서,The method of claim 7, wherein 상기 포토레지스트 수지는 통상의 포토레지스트용 중합체를 포함하는 것을 특징으로 하는 조성물.The photoresist resin composition, characterized in that it comprises a conventional photoresist polymer. 제 7 항에 있어서,The method of claim 7, wherein 상기 포토레지스트 수지는 하기 화학식 12로 표시되는 폴리(바이싸이크로[2,2,2]헵트-5-엔/2-하이드록시에틸바이싸이크로[2,2,1]헵트-5-엔 2-카르복실레이트/말레익안하이드라이드)인 것을 특징으로 하는 포토레지스트 조성물.The photoresist resin is a poly (bicyclo [2,2,2] hept-5-ene / 2-hydroxyethylbicyclo [2,2,1] hept-5-ene 2 represented by Formula 12 below. Carboxylate / maleic hydride). ＜화학식 12＞<Formula 12> 제 7 항에 있어서,The method of claim 7, wherein 상기 광산발생제는 디페닐요도염 헥사플루오르포스페이트, 디페닐요도염 헥사플루오르 아르세네이트, 디페닐요도염 헥사플루오르 안티모네이트, 디페닐파라메톡시페닐 트리플레이트, 디페닐파라톨루에닐 트리플레이트, 디페닐파라이소부틸페닐 트리플레이트, 디페닐파라-t-부틸페닐 트리플레이트, 트리페닐설포늄 헥사플루오르 포스페이트, 트리페닐설포늄 헥사플루오르 아르세네이트, 트리페닐설포늄 헥사플루오르 안티모네이트, 트리페닐설포늄 트리플레이트 및 디부틸나프틸설포늄 트리플레이트로 이루어진 군으로부터 선택된 1 또는 2 이상인 것을 특징으로 하는 포토레지스트 조성물.The photoacid generator is diphenyl iodo hexafluorophosphate, diphenyl iodo hexafluoro arsenate, diphenyl iodo hexafluoro antimonate, diphenyl paramethoxyphenyl triflate, diphenyl paratoluenyl triflate, diphenyl Paraisobutylphenyl triflate, diphenylpara-t-butylphenyl triflate, triphenylsulfonium hexafluoro phosphate, triphenylsulfonium hexafluoro arsenate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium Photoresist composition, characterized in that 1 or 2 or more selected from the group consisting of triflate and dibutylnaphthylsulfonium triflate. 제 7 항에 있어서,The method of claim 7, wherein 상기 유기용매는 시클로헥사논, 메틸 3-메톡시프로피오네이트, 에틸 3-에톡시프로피오네이트 및 프로필렌글리콜 메틸에테르 아세테이트로 이루어진 군으로부터 선택된 것을 특징으로 하는 포토레지스트 조성물.The organic solvent is selected from the group consisting of cyclohexanone, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate and propylene glycol methylether acetate. (a) 제7항 기재의 조성물을 소정의 피식각층 상부에 도포하는 단계와,(a) applying the composition of claim 7 on top of a predetermined etched layer, (b) 노광장치를 이용하여 상기 기판을 노광하는 단계와,(b) exposing the substrate using an exposure apparatus; (c) 상기 결과물을 현상하는 단계를 포함하는 것을 특징으로 하는 포토레지스트 패턴 형성방법.and (c) developing the resultant photoresist pattern. 제 12 항에 있어서,The method of claim 12, 상기 노광장치는 ArF광(193nm), KrF광(248nm), E-빔, X-레이, EUV 및 DUV(deep ultra violet)로 이루어진 군으로부터 선택된 노광원을 사용하는 것을 특징으로 하는 방법.And the exposure apparatus uses an exposure source selected from the group consisting of ArF light (193 nm), KrF light (248 nm), E-beam, X-ray, EUV and deep ultra violet (DUV). 제 12 항에 있어서,The method of claim 12, 상기 현상 공정은 알카리 현상액을 사용하여 수행하는 것을 특징으로 하는 방법.Wherein said developing step is performed using an alkaline developer. 제 14 항에 있어서,The method of claim 14, 상기 알카리 현상액은 2.38% 또는 2.5% TMAH수용액인 것을 특징으로 하는 방법.The alkaline developer is 2.38% or 2.5% TMAH aqueous solution. 제 14 항에 있어서,The method of claim 14, 상기 (b)단계의 전 및/또는 후에 베이크 공정을 더 포함하는 것을 특징으로 하는 방법.And before and / or after the step (b). 제 16 항에 있어서,The method of claim 16, 상기 베이크 공정은 70 내지 200℃에서 1 내지 5분간 수행되는 것을 특징으로 하는 방법.The baking process is characterized in that performed for 1 to 5 minutes at 70 to 200 ℃. 제 12 항에 있어서,The method of claim 12, 상기 포토레지스트 패턴은 네가티브 패턴인 것을 특징으로 하는 방법.And wherein said photoresist pattern is a negative pattern. 제12항 기재의 방법에 의해 제조된 반도체 소자.A semiconductor device manufactured by the method of claim 12.
KR10-1998-0051355A 1998-11-27 1998-11-27 Novel Photoresist Crosslinkers and Photoresist Compositions Using Them KR100400296B1 (en)

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KR10-1998-0051355A KR100400296B1 (en) 1998-11-27 1998-11-27 Novel Photoresist Crosslinkers and Photoresist Compositions Using Them
US09/448,916 US6368773B1 (en) 1998-11-27 1999-11-24 Photoresist cross-linker and photoresist composition comprising the same
DE19956531A DE19956531A1 (en) 1998-11-27 1999-11-24 Crosslinker for a photoresist and a photoresist composition containing the same
GB9927637A GB2344104B (en) 1998-11-27 1999-11-24 Photoresist composition comprising a cross-linker
FR9914920A FR2786491B1 (en) 1998-11-27 1999-11-26 CROSSLINKING AGENT FOR PHOTORESIST, AND PHOTORESIST COMPOSITION COMPRISING SAME
CNB991258568A CN1163796C (en) 1998-11-27 1999-11-26 Cross linking agent for photoslushing compound, and photoslushing compound compsns. containing same cross linking agent
IT1999TO001042A IT1308659B1 (en) 1998-11-27 1999-11-26 CROSS-LINKING FOR PHOTORESIST AND PHOTORESIST COMPOSITION INCLUDING LOSTESSO.
NL1013685A NL1013685C2 (en) 1998-11-27 1999-11-26 Photoresist crosslinker and photoresist composition comprising it.
TW088120825A TW459010B (en) 1998-11-27 1999-11-26 Cross-linker for photoresist, and photoresist composition comprising the same
JP33865999A JP4127941B2 (en) 1998-11-27 1999-11-29 Photoresist composition, method for forming photoresist pattern, and method for manufacturing semiconductor device

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KR100533361B1 (en) * 1999-08-23 2005-12-06 주식회사 하이닉스반도체 Organic polymer used for prevention of random reflection and process for preparation thereof
KR100557585B1 (en) * 1999-10-29 2006-03-03 주식회사 하이닉스반도체 Photoresist composition for resist flow process and process for forming a contact hole using the same
KR100557608B1 (en) * 1999-02-10 2006-03-10 주식회사 하이닉스반도체 Novel photoresist crosslinker and photoresist composition using the same
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US7749680B2 (en) 2007-01-05 2010-07-06 Hynix Semiconductor Inc. Photoresist composition and method for forming pattern of a semiconductor device
CN113321663A (en) * 2021-06-23 2021-08-31 徐州博康信息化学品有限公司 Main chain degradable photoresist resin monomer synthesized from 1, 3-dihydroxyacetone dimer and synthesis method and application thereof

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KR100533361B1 (en) * 1999-08-23 2005-12-06 주식회사 하이닉스반도체 Organic polymer used for prevention of random reflection and process for preparation thereof
KR100557585B1 (en) * 1999-10-29 2006-03-03 주식회사 하이닉스반도체 Photoresist composition for resist flow process and process for forming a contact hole using the same
KR100866748B1 (en) * 2007-01-05 2008-11-03 주식회사 하이닉스반도체 Photoresist composition and method for forming pattern
US7749680B2 (en) 2007-01-05 2010-07-06 Hynix Semiconductor Inc. Photoresist composition and method for forming pattern of a semiconductor device
CN113321663A (en) * 2021-06-23 2021-08-31 徐州博康信息化学品有限公司 Main chain degradable photoresist resin monomer synthesized from 1, 3-dihydroxyacetone dimer and synthesis method and application thereof
CN113321663B (en) * 2021-06-23 2022-07-22 徐州博康信息化学品有限公司 Main chain degradable photoresist resin monomer synthesized from 1, 3-dihydroxyacetone dimer and synthesis method and application thereof

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